1,3-diarylhexahydroindazole derivatives as optical brighteners

ABSTRACT

THE PRESENT INVENTION RELATES TO NEW 1,3-DIARYL-3A,4,5,6, 7,7A-HEXAHYDROINDAZOLES, WHICH ARE USEFUL AS OPTICAL BRIGHTENERS FOR HIGH MOLECULAR ORGANIC MATERIALS. SAID COMPOUNDS ARE OF THE FORMULA   1-(3-R2,4-R1-PHENYL),3-(3-R6,4-R7-PHENYL),4,7-(-X-),5-R5,   6-R3,6-R4,3A,4,5,6,7,7A-HEXAHYDROINDAZOLE   OR POSITIONAL ISOMERS OF R3 AND R4 WITH R5, WHEREIN R1 REPRESENTS TRIFLUOROMETHYL, NITRILE, A -COOR,   -CO-N(-R)-R&#39;&#39; OR -SO2-N(-R)-R&#39;&#39;   RADICAL, WHREIN R AND R&#39;&#39; INDEPENDENTLY OF ONE ANOTHER REPRESENT HYDROGEN, OR ALKYL CONTAINING 1-4 CARBON ATOMS AND OPTIONALLY SUBSTITUTED BY HYDROXYL, ALKOXY, AMINO, SULPHONIC ACID OR CARBOOXYLIC ACID, OR R AND R&#39;&#39; TOGETHER WITH THE NITROGEN REPRESENT PYRROLIDINO OR OPTIONALLY METHYL-SUBSTITUTED MORPHOLINO OR PIPERIDINO, OR THE -SO2R&#34; RADICAL, WHEREIN R&#34; REPRESENTS ALKYL WITH 1 TO 4 CARBON ATOMS OOPTIONALLY SUBSTITUTED BY HYDROXYL, ALKOXY, AMINO, SULPHONIC ACID OR CARBOXYLIC ACID, OR REPESENT ALKENYL WITH 2 TO 4 C ATOMS OR ARYL, R2 DENOTES HYDROGEN, CHLORINE OR ALKYL CONTAINING 1 TO 3 CARBON ATOMS, R3 R4 AND R5 INDEPENDENTLY ON ONE ANOTHER DENOTE HYDROGEN, NITRILE, ALKYL POSSESSING 1 TO 4 CARBON ATOMS, A-COOY OR   -CO-N(-Y)-Y&#39;&#39;   RADICAL, WHEREIN Y AND y&#39;&#39; INDEPENDENTLY OF ONE ANOTHER REPRESENT HYDROGEN OR ALKYL WITH 1 TO 4 CARBON ATOMS OPTIONALLY SUBSTITUTED BY HYDROXYL, OR Y AND Y&#39;&#39; TOGETHER WITH THE NITROGEN REPRESENT PYRROLIDINO OR OPTIONALLY METHYL-SUBSTITUTED PIPERIDINO OR MORPHOLINO, OR R4 AND R5 TOGETHER DENOTE A FUSED BENZENE RING OPTIONALLY CONTAINING NON-CHROMOPHOORIC SUBSTITUENTS, R6 AND R7 INDEPENDENTLY OF ONE ANOTHER DENOTE HYDROGEN, AHLOGEN UP TO ATOMIC NUMBER 35 OR ALKYL POSSESSSING 1 TO 4 CARBON ATOMS AND X DENOTES -CH2, -O-OR-NZ-, WHEREIN Z REPRESENTS ALKYL WITH 1 TO 4 CARBON ATOMS.

United States Patent Oflice 3,828,069 Patented Aug. 6, 1974 3,828,069 1,3-DIARYLHEXAHYDROINDAZOLE DERIVA- TIVES AS OPTICAL BRIGHTENERS Mauro Stagi, Allschwil, Switzerland, assignor to Ciba- Geigy AG., Basel, Switzerland No Drawing. Filed Apr. 5, 1972, Ser. No. 241,385 Claims priority, application Switzerland, Apr. 19, 1971, 5,632/71 Int. Cl. C07d 49/10 US. Cl. 260-310 D 2 Claims ABSTRACT OF THE DISCLOSURE R C 2 II a N or positional isomers of R and R, with R wherein R represents trifluoromethyl, nitrile, a COOR,

radical, wherein R and R independently of one another represent hydrogen, or alkyl containing 1-4 carbon atoms and optionally substituted by hydroxyl, alkoxy, amino, sulphonic acid or carboxylic acid, or R and R together with the nitrogen represent pyrrolidino or optionally methyl-substituted morpholino or piperidino, or the SO R" radical, wherein R" represents alkyl with 1 to 4 carbon atoms optionally substituted by hydroxyl, alkoxy, amino, sulphonic acid or carboxylic acid, or represents alkenyl with 2 to 4 C atoms or aryl, R denotes hydrogen, chlorine or alkyl containing 1 to 3 carbon atoms, R R and R independently of one another denote hydrogen, nitrile, alkyl possessing 1 to 4 carbon atoms, a COOY or radical, wherein Y and Y independently of one another represent hydrogen or alkyl with 1 to 4 carbon atoms optionally substituted by hydroxyl, or Y and Y' together with the nitrogen represent pyrrolidino or optionally methyl-substituted piperidino or morpholino, or R and R together denote a fused benzene ring optionally containing non-chromophoric substituents, R and R independently of one another denote hydrogen, halogen up to atomic number 35 or alkyl possessing 1 to 4 carbon atoms and X denotes CH -O- or NZ, wherein Z represents alkyl with 1 to 4 carbon atoms.

The present invention relates to new 1,3-diaryl3a,4,5, 6,7,7a-hexahydroindazole compounds, processes for their manufacture, their use for the optical brightening of synthetic and natural high molecular organic material, preferably in the form of fibres or fabrics, and their use as an additive in detergents and soaps.

It has now been found, surprisingly, that 1,3-diaryl- 3a,4,5,6,7,7a-hexahydroindazoles in which the phenyl ring is substituted by specific groups in the 1-position, are valuable optical brighteners having a neutral white shade.

The optical brighteners according to the invention correspond to the formula or positional isomers of R and R, with R wherein R represents trifluoromethyl, nitrile, a COOR,

B R CON or SOzN radical, wherein R and R independently of one another represent hydrogen, or alkyl containing 1-4 carbon atoms and optionally substituted by hydroxyl, alkoxy, amino, sulphonic acid or carboxylic acid, or R and R together with the nitrogen represent pyrrolidino or optionally methyl-substituted morpholino or piperidino, or the SO radical, wherein R represents alkyl with 1 to 4 carbon atoms optionally substituted by hydroxyl, alkoxy, amino, sulphonic acid or carboxylic acid, or represents alkenyl with 2 to 4 C atoms or aryl, R denotes hydrogen, chlorine or alkyl containing 1 to 3 carbon atoms, R R and R independently of one another denote hydrogen, nitrile, alkyl possessing 1 to 4 carbon atoms, a COOY or radical, wherein Y and Y' independently of one another represent hydrogen or alkyl with l to 4 carbon atoms optionally substituted by hydroxyl, or Y and Y together with the nitrogen represent pyrrolidino or optionally methyl-substituted piperidino or morpholino, or R and R together denote a fused benzene ring optionally containing non-chromophoric substituents, R and R independently of one another denote hydrogen, halogen up to atomic number 35 or alkyl possessing 1 to 4 carbon atoms and X represents CH O- or NZ, wherein Z represents alkyl with l to 4 carbon atoms.

Possible non-chromophoric substituents on the fused benzene ring are above all alkyl, such as methyl and ethyl, alkoxy, such as methoxy and ethoxy, and halogen, such as chlorine.

Within the framework of the formula (I), compounds of predominant interest are those of the formula 3 or positional isomers, of R and R with R12 wherein R denotes nitrile, the

Q CON radical, wherein Y and Y independently of one another represent hydrogen or optionally hydroxyl-substituted alkyl possessing 1 to 4 carbon atoms, or Y and Y together with the nitrogen represent pyrrolidino or optionally methyl-substituted piperidino or morpholino, or R and R together denote a fused benzene ring, R and R independently of one another denote hydrogen, chlorine or alkyl with 1 to 3 carbon atoms and X denotes CH --O-- or NZ-, wherein Z represents alkyl with 1 to 4 carbon atoms.

Preferred compounds correspond to the formula 'W EZ or positional isomers of R and R with R wherein R denotes hydrogen or nitrile, R denotes nitrile, methylsulphonyl, carboxyl or carbalkoxy with 2 to carbon atoms, R and R independently of one another denote hydrogen, nitrile, alkyl with 1 to 4 carbon atoms, or carboxyl, optionally hydroxyl-substituted carbalkoxy with 2 to 5 carbon atoms or carbamoyl or R and R denote a fused benzene radical, R denotes hydrogen, chlorine or methyl and X denotes 1 Compounds of outstanding practical interest are the indazoles of the formula or positional isomers of R and R with R wherein R denotes hdrogen or nitrile, R denotes nitrile or methylsulphonyl, R denotes hydrogen, nitrile, carboxyl, optionally hydroxyl-substituted carbalkoxy with 2 to 5 carbon atoms or carbamoyl, R denotes hydrogen or carbalkoxy with 2 to 5 carbon atoms or R and R together denote a fused benzene radical, R denotes hydrogen or chlorine and X denotes CH or O--.

If a benzene radical is not fused to the bicycloheptane system, one each of the substituents R and R R and R R and R or R and R in the formulae (1), (2), (3) and (4) preferably represents a substituent other than nitrile,

/Y COOY or CON that is to say it represents alkyl or especially hydrogen. The compounds according to the invention, of the formula (I), can be obtained in accordance with processes which are in themselves known, such as are described, for example, in Tetrahedron, 1962, Volume 17, page 3 to 29. The process which in practice is most important for the manufacture of the compounds of the formula (I) is characterised in that an ot-halogeno-arylaldehydehydrazone of the formula Ra 3a=am t wherein R R R and R7 have the indicated meaning, is reacted with a bicycloheptene of the formula wherein X, R R and R have the indicated meaning, in accordance with the principle of a l-3-dipolar addition. The reaction is advantageously carried out in an organic solvent which is inert towards the reactants and in the presence of an acid acceptor, at temperatures of 0-100", preferably at 20 to 50 C.

Suitable solvents are above all optionally halogenated aromatic or aliphatic hydrocarbons, such as, for example, benzene, toluene, xylenes, chlorobenzene, dichlorobenzene, hexane, ligroin, methylene chloride, ethylene chloride, carbon tetrachloride and ethers for example, dioxane or diethyl ether.

Possible acid acceptors are NaOH, KOH and above all tertiary amines, such as triethylamine, diethylaniline or pyridine. In general, 1 to 10, preferably 1 to 5, equivalents of acid acceptor are employed per equivalent of hydrogen.

The whalogeno-aryl-aldehyde-arylhydrazones of the formula (5) required as starting materials are manufactured in the usual manner.

Equally, the bicycloheptenes of the formula (6) are manufactured in accordance with known processes, in particular by a Diels-Alder addition of cyclopentadiene or furane or pyrrole to an activated ethylene bond in accordance with the following equation:

Ra a

The new indazoles of the formula (1) are colourless, well-crystallised substances which are sparingly soluble to insoluble in hot water. They dissolve in organic solvents, for example in alkanols, lower fatty acids, lower fatty acid esters, lower fatty acid amides, lower ketones and in optionally halogenated aromatic hydrocarbons. The practically colourless organic solutions are distinguished by vivid violet to blue fluorescence.

'The new indazoles are suitable for the optical brightening of high molecular organic material. Possible high molecular organic materials are above all synthetic organic polyplasts, that is to say plastics obtainable by polycondeusation and polyaddition, for example, polyolefines, such as polyethylene, polypropylene or polystyrene, and also polyvinyl chloride, polyacrylonitrile and its copolymers, polyurethanes, polyamides and cellulose esters.

The optical brightening of the high molecular organic material is effected, for example, by incorporating therein small amounts of optical brighteners according to the invention, for example 0.0001 to 2%, preferably 0.001 to 0.3%, relative to the material to be brightened, optionally together with other substances, such as plasticisers, pigments and the like. Depending on the nature of the material to be brightened, this is done by dissolving the brightener in the monomers before polymerisation, in the mass of the polymer or, together with the polymer, in a solvent. The material pretreated in this way is thereafter converted to the desired ultimate shape in accordance with processes which are in themselves known, such as calendering, pressing, extrusion, spreading, casting or injection moulding.

Preferably, however, high molecular organic material in the form of fibres is brightened, for example fibre material of polyamide, polyacrylonitrile and its copolymers, cellulose esters, such as cellulose acetates. Advantageously, an aqueous dispersion of indazoles according to the invention, of the formula (I), is used for the brightening of these fibre materials. The brightener dispersion here preferably contains 0.01-0.2% of indazole according to the invention, relative to the fibre material. In addition, it can contain auxiliaries, such as dispersing agents, for example condensation products of fatty alcohols possessing to 18 carbon atoms with to 25 mols of ethylene oxide, or condensation products of alkylmonoamines or polyamines possessing 16 to 18 carbon atoms with at least 10 mols of ethylene oxide and, where fibre material of polymeric or copolymeric acrylonitrile is brightened, also acids, especially organic acids, such as acetic, oxalic and preferably formic acid.

The brightening of the fibre material with the aqueous brightener dispersion is effected either by the exhaustion process at temperatures of, preferably, 60 to 100 C. or by the padding process. In the latter case, the goods are impregnated with the brightener dispersion and are finished by, for example, steaming at 70 to 100 0., preferably with saturated neutral steam. The finished fibre material is finally rinsed and dried. Preferably the fibre material mentioned is brightened by the exhaustion process.

High molecular organic material optically brightened in accordance with the invention, especially the synthetic fibre material brightened in accordance with the exhaustion process, shows an attractive pure white appearance with a bluish-tinged fluorescence.

Indazoles according to the invention can also be used for the optical brightening of detergents, for example soaps, soluble salts of fatty alcohol sulphates, higher alkyl-substituted and/or multiple-alkyl substituted aryl sulphonic acids, sulphonic-carboxylic acid esters of medium to higher alkanols, higher alkanoyl-aminoalkylor aminoaryl-carboxylic acids or -sulphonic acids or fatty acid glycerine-sulphates, as well as non-ionic detergents, such as higher alkylphenol-polyclycol-ethers.

Detergents according to the invention can contain the customary fillers and auxiliaries, for example alkali polyphosphates, and polymetaphosphates, alkali silicates, alkali borates, alkali salts of carboxymethylcelluloses, foam stabilisers, such as alkanolamides of higher fatty acids, or complexones, such as soluble salts of ethylene-drammetetraacetic acid.

The new indazoles are appropriately incorporated into the detergents or into washing liquors in the form of their solutions in neutral organic solvents which are miscible with water and/or are easily volatile, such as lower alkanols, lower alkoxyalkanols, lower fatty acid amides or lower aliphatic ketones. They can, however, also be used in a finely divided solid form, by themselves or mixed with dispersing agents. For example, they can be mixed, kneaded or ground with the detergent substances and the customary auxiliaries and fillers can then be mixed in. For example, the brighteners are stirred with the detergent substances, customary auxiliaries and fillers and water to give a paste, and this paste is then sprayed 1n a spray drier. The new indazole derivatives can also be mixed with finished detergents, for example by spraying a solution in an easily volatile and/or water-soluble organic solvent onto the dry agitated detergents. The content of optical brightener of the formula (1) in the detergents is advantageously 0.001-0.5% relative to the solids content of the detergent.

Wash liquors which contain indazoles according to the invention, of the formula (1), on washing impart a brilliant appearance in daylight to the textile fibres treated therewith, for example synthetic polyamide and cellulose ester fibres. They can therefore be used particularly for washing these synthetic fibres or the textiles or textile components consisting of such fibres, and for laundry. For use in household laundry, they can additionally contain yet further optical brighteners possessing an aifinity for other fibres, for example for cellulose.

In order to achieve a particular white shade it often proves advisable to employ mixtures of hexahydroindaa zoles according to the invention. Such mixtures can be purely mechanical mixtures of the individual components or can be actual crystal compounds of which the crystal structure is different from those of the individual components. Such a mixture can be manufactured by dry mixing, fusing together or conjoint recrystallisation of the individual components.

By positional isomers of R and R, with R compare formula (1), there are to be understood compounds of the formula 1'1 ILL X R3 R wherein R to R and X have the indicated meaning. A remark in the same general sense applies also to the compounds of the formulae (2) to (4) as well as (10), and accordingly to the examples of the formulae (12) to (34) and (43) to (59).

EXAMPLE 1 parts of tot-chloro-[(4-chloro)-benzaldehyde-(4'- cyanophenyl) l-hydrazone and 79 parts of norbornene are suspended in 1,500 parts of toluene. parts of triethylamine are added dropwise at 50-60" C. and the mixture is stirred for a further 3 hours at this temperature. Thereafter the suspension is cooled, the triethylamine hydrochloride is filtered oif and the filtrate is evaporated. The residue is then crystallised from isopropanol. In this way, 77 parts of the compound of the formula of melting point 194-195 C. are obtained.

The new compound fluoresces with an intense blueviolet colour in organic solvents. It is above allsuitable for the optical brightening of polyamide, polyacrylonitrile, cellulose acetate and wool.

EXAMPLE 2 If instead of oz-chloro-[(4-chloro)-benzaldehyde-(4- cyanophenyl)]-hydrazone equimolar amounts of substituted a-chlorohydrazones of the formula I are used and instead of norbornene the substituted norbornenes of the formula I II are used and in other respects the procedure of Example 1 is followed, the substituted hexahydroindazoles of the formula a m lm r positional isomers of V and V with V of Table I are obtained.

The new compound fluoresces with a very intense blueviolet colour in organic solvents and is suitable for the optical brightening of polyamide, cellulose acetate and wool.

EXAMPLE 4 If in Example 1, instead of norbornene, equimolar amounts of 1,4-dihydro-1,4-epoxynaphthalene are employed, the compound of the formula of melting point 200-20l C. is obtained in highyield. The new compound is above all suitable for the brightening of polyamide and cellulose acetate.

EXAMPLE 5 TABLE I Melting Percent Compound of point, exo, the Formula V1 V1 V1 V V5 C. endo (11) SOQCH! H H H H 237-238 (12) SOrCHu 01 CN H H 25 ea. (13) SOzCHa Cl H ON H 238-240 ca. 90 S CH: Cl CN OH; H 250 SO2CH3 H H COOH H 250 S02CHa C1 H COOH H CH: 01 H COOCH; H 802GB: H H COOCH: H 20H; Cl H ONH-z H H H H COOCHzCHzOH H SO2CH3 Cl H COOH SOzCHa Cl H COOCqHn 020E! Cl H COOCH:

H H H C1 CN H Cl H ON Cl CN CH: Cl H GOOH 01 H CONH: Cl H COOCH: Cl H OOOH Cl H 0000411! 01 H 0C 1 EXAMPLE 3 If, in Example 1, instead of norbornene equimolar 6 amounts of 3,6-oxa-4-carbomethoxy-cyclohexene are employed, the compound of the formula N Waco-on,

zone and 1,4-dihydro-1,4methanonaphthalene are emof melting point 172174 C. is obtained.

of melting point 260 C. is obtained in high yield.

EXAMPLE 6 If in Example 4 a-chloro-benzaldehyde-phenylhydra- 9 10 ployed as the reaction components, the compound of the 50 C. The mixture is thereafter stirred for a further 3 formula hours, the solvent is distilled off in vacuo and the residue (37) is washed with cold water, thoroughly suction-filtered off and dried in vacuo. The dried product is thereafter boiled 5 for hours under reflux with 50 parts of methanol and 0.5 part of p-toluenesulphonic acid. The compound of the H l formula N of'melting point 180 C. is obtained.

EXAMPLE 7 If the same procedure as in Example 1 is followed but 15.4 parts of a-chlorobenzaldehyde-(4-methylsulpho- 802cm phenyl)-hydrazone and 19.9 parts of 1,4-dihydro-1,4- methane-naphthalene are employed, the compound of the formula is thus obtained. It shows an absorption maximum in dioxane at 370 nm. and fluoresces with an intense blueviolet colour in organic solvents.

The intermediate product OzCHa Y is obtained in good yield. The analytically pure compound is obtained by the reaction of maleic anhydride with a obtained by recrystallisation from toluene melts at above four-fold 1m0l1nt 0f Y Py at room p? 260 C. and shows excellent brightener effects in plastic ture- Thllght Yellow cfystalllne Compound SubllIIleS I hcompositions. out melting.

' EXAMPLE 8 EXAMPLE 9 7 parts of a-ChlOIO/ (4-chloro)-benzaldehyde-(4-meth- The Compounds of the fOrmula ylsulphophenyl)/-hydrazone and 7.2 parts of the com- 40 42 pound m-Q-C U; (39) II I? t; N

45 l N-CH3 O II I I 0 1 are suspended in 50 parts of toluene and 9 parts of trilisted in the table which follows are obtained in analogous ethylamine are added over the course of 30 minutes at Ways to those described in Examples 1-8.

TABLE Compound of the Formula U1 U2 U3 U4 5 Us U1 Z CN --H CN H H 01 CH5 CH2 COOH -Cl COOCHa H COOCH; H 01 CH COOCH; H CN CN -CN H H CHP --COOOH2CHOH H CN CN CH; H Cl CHF 47.... CON(CH;)3 H CON 0 H COOCH; H CH3 -CH- 48 SO2CH3 OH; COOCHa H COOCH; 01 CH; -O- 49 SOzNHa H COOCHa H COOCH; H 01 N-CH,

50.4---- SOzN(CHa)2 H "ZS-T3221"; H CH; 0

51 CFg H H H H Cl -H CH1- 52 COOC2H4OCH3 01 CN CH: H H H CH2 53 COOC2H4N O H H -H H H H -CHr- 54 -SO1CH=CH5 H --COOC4H9 H COOCJI H Cl -O- 55 -so2oH2oH2oH H 420001120112)? 6 H coocmoHm o 01-11 -cH- TABLECon tinued Compound of the Formula U1 U3 U3 U4 Us U U Z 56 SO CH CH 050 H -H H -H -H H -Cl CH2- 5? SOZCZ |OC HCH 2N(CH -H -H -H --H -H -Cl CH2 58 -SO2N O -H -CON -H COOCH3 -Cl CH CH2- 59--.'.--- Same as 8bOVB.T'- .'.'ZILIT.".TIIL'. --H -CON -H -COOCH; --C1 -CH -CH2 EXAMPLE 1U EXAMPLE 12 Brightening of Nylon in a Washing Bath 0.4 g. of detergent of the following composition are added to 100 ml. of water:

*(Instead of Glaubers salt, the detergent can also contain 10-20% of Na perborate or of some other oxygen-donating agent).

A solution of the optical brightener of the formula (7) is prepared by dissolving 1 g. in 1,000 ml. of dimethylformamide. 2 ml. of this stock solution are added to the solution described above. This aqueous solution (or dispersion) containing the brightener is warmed to 60 C. A nylon fabric weighing 3 g. is then introduced into the solution and is treated at this temperature for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for minutes at 60 C.

The-fabric treated in this way shows a distinct brightening effect.

Identical effects are obtained if instead of the compound of the formula (7) a compound of the formula (18), (20), (22), (24), or (33) is employed.

EXAMPLE ll Brightening of Polyamideby the Exhaustion Process under Acid Conditions 0.12 ml. of 85% strength formic acid and 0.06 g. of Tinegal NA ('=alkyl-polyglycol-ether) are added to 100 ml. of water.

A solution of the optical brightener of the formula (24) is prepared by dissolving 1 g. in 1,000 ml. of dimethylformamide. 3 ml. of this stock solution are added to the solution described above. This aqueous solution or dispersion containing the brightener is warmed to 60 C. and a polyamide fabric weighing 3 g. is then introduced into the solution. The temperature is raised to 92-95 C. over the course of 10-15 minutes and is maintained thereat for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60 C.

The fabric treated in this way shows a distinct brightening effect.

Equally good results are obtained if instead of the compound of the formula (24) a compound of the formula (26), (27), (30) or (32) is employed.

Brightening of Polyamide by the Exhaustion Process under Neutral Conditions i 0.06 g. of Tinegal NA (=alkyl-polyglycol-ether) is added to 100 ml. of water.

A solution of the optical brightener of the formula (13) is prepared by dissolving 1 g. in 1,000 ml. of dimethylformamide. 3 ml. of this stock solution are added to the solution described above. This aqueous solution or dispersion containing the brightener is warmed to 60 C. and a nylon fabric weighing 3 g. is then introduced into the solution. The temperature is raised to 92-95 C. over the course of 10-15 minutes and is kept thereat for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60 C.

The fabric treated in this way shows a distinct brightening effect.

If the compound of the formula (13) is replaced by a compound of the formula (7), (l4), (17), (18), (20), (22), (23), (24), (25), (26), (27), (30) or (33), similar results are obtained.

EXAMPLE l3 Brightening of Orion by the Exhaustion Process under Acid Conditions 0.12 ml. of strength formic acid and 0.06 g. of Tinegal NA (==alkyl-polyglycol-ether) are added to 100 ml. of water.

A solution of the optical brightener of the formula (17) is prepared by dissolving 1 g. in 1,000 ml. of di methylformamide. 1.5 ml. of this stock solution are added to the solution described above. This aqueous solution (or dispersion) containing the brightener is warmed to 60 C. and an Orlon fabric weighing 3 g. is then introduced into the solution. The temperature is raised to 9598 C. over the course of 10-15 minutes and is kept thereat for 60 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 50 C.

The fabric treated in this way shows a distinct brightening effect.

Identical effects are obtained if the compound of the formula (17) is replaced by a compound of the formula (7), (13) or (24).

EXAMPLE 14 Brightening of 2 /z-Acetate by the Exhaustion Process under Acid Conditions 0.06 ml. of 40% strength acetic acid and 0.06 ml. of Tinegal NA (=alkyl-polyglycol-ether) are added to 95 ml. of water.

A solution of the optical brightener of the formula (17) is prepared by dissolving 1 g. in 1,000 ml. of dimethylformamide. 6 ml. of this stock solution are added to the solution described above. This aqueous solution or dispersion containing the brightener is warmed to 40 13 C. and an acetate fabric weighing 3 g. is then introduced into the solution. The temperature is raised to 75-80 C. over the course of 10-15 minutes and is kept thereat for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60 C.

The fabric treated in this way shows a distinct Identical effects are obtained with the compounds of the formulae (7), (13), (14), (17), (24), (2.7), (30) or (33).

EXAMPLE 15 Brightening of Triacetate by the Exhaustion Process under Acid Conditions 0.06 ml. of 40% strength acetic acid and 0.06 ml. of Tinegal NA (-=alkyl-polyglycol-ether) are added to 95 ml. of water.

A solution of the optical brightener of the formula (13) is prepared by dissolving 1 g. in 1,000 ml. of dimethylformamide. 6 ml. of this stock solution are added to the solution described above. The aqueous solution or dispersion containing the brightener is warmed to 60 C. and a triacetate fabric weighing 3 g. is then introduced into the solution. The temperature is raised to 95-98" C. over the course of 10-15 minutes and is kept thereat for 30 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60 C.

The fabric treated in this way shows a distinct brightening effect.

Similar results are obtained if instead of the compound of the formula (13) a compound of the formula (7), (17), (24), (25), (30) or (32) is used.

EXAMPLE 16 Brightening of Wool in a Reducing Bleach Bath under Neutral Conditions 0.36 g. of Clarit PS andin the case of water-insoluble brightenersadditionally 0.06 g. of Tinegal NA (-=alkyl-polyglycol-ether) are added to 110 ml. of water.

A solution of the optical brightener of the formula (30) is prepared by dissolving 1 g. in 1,000 ml. of dimethylformamide. 7.5 ml. of this stock solution are added to the solution described above. This aqueous solution (or dispersion) containing the brightener is warmed to 40 C. and a pre-bleached woolen fabric or yarn weighing 3 g. is then introduced into the solution. The temperature is raised to 60 C. over the course of 10-15 minutes and is kept thereat for 60 minutes. The fabric is then rinsed for 2 minutes in running cold water and is subsequently dried for 20 minutes at 60 C.

The fabric treated in this way shows a distinct brightening effect.

Similar results are obtained with compounds of the formula (7), (13), (18), (24), (25), (32) or (33).

EXAMPLE 17 10,000 parts of a polyamide in chip form, manufactured from e-caprolactam in a known manner, are mixed with 30 parts of titanium dioxide (rutile modification) and 2 parts of the compound of the formula (17 (18), (20), (23), (30), (32) or (33) in a tumbler vessel for 12 hours. After displacing the atmospheric oxygen, the chips treated in this way are fused in a kettle heated to 270 C. and the melt is stirred for half an hour. It is then extruded under a nitrogen pressure of atmospheres gauge through a spinneret and the cooled filament is wound up on a spinning bobbin. The filaments produced show an excellent brightening effect which is resistant to thermofixing and has good fastness to washing and to light.

EXAMPLE 18 An intimate mixture of 100 parts of polyvinyl chloride, 3 parts of stabiliser (Advastat ED 100; Ba/Cd complex), 2 parts of titanium dioxide, 59 parts of dioctyl phthalate and 0.01 to 0.2 part of one of the compounds of the formulae (17), (23), (30), (36) or (38) is milled on a calender at to C. to give a sheet. The opaque polyvinyl chloride sheet thus obtained has a substantially higher degree of whiteness than a sheet which does not contain the optical brightener.

EXAMPLE 19 100 parts of polystyrene and 0.1 part of one of the compounds of the formulae (30), (32), (33) or (37) are fused for 20 minutes at 210 C. in a tube of 1 cm. diameter, with exclusion of air. After cooling, an optically brightened polystyrene composition of good fastness to light is obtained.

EXAMPLE 20 1.5 g. of a delustring agent, 1 g. of titanium dioxide (rutile type) and 0.05 g. of a compound of the formlllae (36), 37) or 38) are stirred into a polyurethane coating composition of 13.3 g. of isocyanate-modified polyester, 26.7 g. of ethyl acetate, 2 g. of reaction accelerator and 2 g. of polyfunctional isocyanate as a crosslinking agent. This mixture is left to stand for 2 hours and is then spread by means of a knife or a film-drawing rod on a cotton fabric (wet film thickness 1 mm.). Thereafter the fabric is dried for 24 hours at room temperature. The fabric coated in this way shows a strong optical brightening effect of good fastness to light.

EXAMPLE 21 A 13% strength casting composition of acetylcellulose in acetone which containsrelative to the dry weight of plastic-2% of anatase (titanium dioxide) as the delustering agent, and 0.04% of the compounds of the formula (38), is cast on a glass plate and spread by means of a metal rod to give a thin film. After drying, the film shows a substantially higher degree of whiteness than a film manufactured in the same way which does not contain an optical brightener.

EXAMPLE 22 7 g. of anatase (TiO followed by 350 g. of acrylonitrile polymer in powder form, are introduced into 1,400 ml. of dimethylformamide. The mixture is converted into a viscous mass using a high speed stirrer. 5 mg. of a compound of the formulae (17), (18), (20), (23), (30), (32), (33), (36), (37) or (38) are dissolved in 50 g. of this 20% strength polyacrylonitrile solution and after removal of the air bubbles the mass is cast on a glass plate and spread by means of a metal rod with 1 mm. thick guide sleeves to give a uniform film. After drying in a stream of air, the film can be pulled off the glass plate. It has a substantially higher degree of whiteness than a film manufactured in the same way which does not contain the optical brightener.

I claim:

1. A 1,3 Diaryl 3a,4,5,6,7,7a hexahydroindazole corresponding to the formula wherein R denotes hydrogen or nitrile, R denotes nitrile, carboxyl or carbalkoxy of 2 to 5 carbon atoms, R and R independently of one another denote hydrogen, nitrile, alkyl of 1 to 4 carbon atoms, or carboxyl,

15 carbalkoxy of 2 to 5 carbon atoms, hydroxyl-substituted carbalkoxy of 2 to 5 carbon atoms or carbamoyl or R and R together with the carbon atoms to which they are attached denote fused benzene, R denotes hydrogen, chlorine or methyl and X denotes -CH:---, -0 or N CH: 2. A compound of claim 1 in which R is ON, X is methylene, R is ydrogen, R is hydrogen, R is COOCH and R is chlorine.

References Cited Huisgen et al.: Chem. Abst., v01. 57, columns 7246- 50 (1962).

Huisgen et al.: Tetrahedron, vol. 17, pp. 3-22 relied on (1962).

Huisgen et a1.: Chem. Abst. vol. 67, N0. 116333y (1967).

Huisgen et aL: Monatsh. Chem., vol. 98, pp. 1618-50 (1967).

Oppolzer: Chem. Abst. v01. 72, No. 43670:: (1970).

Oppolzer: Tetrahedron Letters 1970 (No. 25), pp. 2199-2204.

Raciszewski et al.: J. Amer. Chem. Soc., vol. 91, pp. 4338-4341 (1969).

NATALIE TROUSOF, Primary Examiner US. Cl. X.R.

117-335 T; 252-301.2 W; 260239.9, 247.1, 247.2 A,

15 247.2 B, 247.5 R, 247.5 B, 247.7 K, 293.6, 293.71, 293.89,

326.29, 326.32, 326.62, 326.5 .1, 346.1, 347.3, 347.4, 464, 468 B, 514 B, 557 B, 566 B UNITED STATES PATENT. OFFICE CERTIFICATE OF CORRECTION Patent No. 3,828,069 Dated August 6, 19 74 Inventor(s) MI? g It is certifiedthat error appears in 'the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 2, C01. 15, line 9, change "ydrogen" to hydrogen Signed and sealed this 19th day of November 1974.

(SEAL) Attest: I

McCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer -Commissioner of Patents FORM Po-w5o (10-69) v I UKOMWDC 0 U., GOVERNNENT PRINTING OFFICE Z I," U-J'3Jl 

